Distribution by Scientific Domains
Distribution within Polymers and Materials Science

Kinds of Styrene

  • sodium styrene
  • substituted styrene

  • Terms modified by Styrene

  • styrene butadiene rubber
  • styrene content
  • styrene copolymer
  • styrene copolymerization
  • styrene derivative
  • styrene moiety
  • styrene monomer
  • styrene oxide
  • styrene polymerization
  • styrene sulfonic acid
  • styrene unit

  • Selected Abstracts

    Miscibility and rheological properties of poly(vinyl chloride)/styrene,acrylonitrile blends prepared by melt extrusion

    Hyun Sik Moon
    Abstract Styrene,acrylonitrile (SAN) with acrylonitrile (AN) concentrations of 11.6,26 wt % and ,-methylstyrene acrylonitrile (,MSAN) with a wide range of AN concentrations are miscible with poly(vinyl chloride) (PVC) through solution blending. Here we examine the rheological properties and miscibility of PVC/SAN and PVC/,MSAN blends prepared by melt extrusion for commercial applications. We have investigated the rheological properties of the blends with a rheometer and a melt indexer. The PVC/SAN and PVC/,MSAN blends have a low melting torque, a long degradation time, and a high melt index, and this means that they have better processability than pure PVC. The miscibility of the blends has been characterized with differential scanning calorimetry, dynamic mechanical thermal analysis, and advanced rheometrics expansion system analysis. The miscibility of the blends has also been characterized with scanning electron microscopy. The SAN series with AN concentrations of 24,31 wt % is immiscible with PVC by melt extrusion, whereas ,MSAN with 31 wt % AN is miscible with PVC, even when they are blended by melt extrusion, because of the strong interaction between PVC and ,MSAN. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 2007 [source]

    Cross-Linked Poly(4-vinylpyridine/styrene) Copolymers as a Support for Immobilization of Ytterbium Triflate.

    CHEMINFORM, Issue 31 2005
    Byoung Se Lee
    No abstract is available for this article. [source]

    Effect of montmorillonite on properties of styrene,butadiene,styrene copolymer modified bitumen

    Jianying Yu
    Clay/styrene,butadiene,styrene (SBS) modified bitumen composites were prepared by melt blending with different contents of sodium montmorillonite (Na-MMT) and organophilic montmorillonite (OMMT). The structures of clay/SBS modified bitumen composites were characterized by XRD. The XRD results showed that Na-MMT/SBS modified bitumen composites may form an intercalated structure, whereas the OMMT/SBS modified bitumen composites may form an exfoliated structure. Effects of MMT on physical properties, dynamic rheological behaviors, and aging properties of SBS modified bitumen were investigated. The addition of Na-MMT and OMMT increases both the softening point and viscosity of SBS modified bitumens and the clay/SBS modified bitumens exhibited higher complex modulus, lower phase angle. The high-temperature storage stability can also be improved by clay with a proper amount added. Furthermore, clay/SBS modified bitumen composites showed better resistance to aging than SBS modified bitumen, which was ascribed to barrier of the intercalated or exfoliated structure to oxygen, reducing efficiently the oxidation of bitumen, and the degradation of SBS. POLYM. ENG. SCI., 47:1289,1295, 2007. © 2007 Society of Plastics Engineers [source]

    Optimization of physico-mechanical properties of silica-filled NR/SBR compounds

    D. Salimi
    Abstract In this extended study, the effect of silica reinforcement on natural rubber (NR) and NR/styrene,butadiene rubber (SBR) compounds was studied. The silica surfaces were treated with bis(3-triethoxysilylpropyl)-tetrasulfide, which is a silane-coupling agent, to chemically bond the silica to the rubber. Optimum levels of silane were determined according to the silica loading in NR compounds. Results in NR/SBR compounded with optimum levels of silane show that the cure time decreases with increasing NR content. Also, the tensile properties of the NR/SBR blends decrease with increasing SBR content. This study further confirmed that filler materials affect the physical and mechanical properties of these blends. © 2010 Wiley Periodicals, Inc. Adv Polym Techn 28:224,232, 2009; Published online in Wiley InterScience ( DOI 10.1002/adv.20169 [source]

    A Polymer-Bound Oxidovanadium(IV) Complex Prepared from an L -Cysteine-Derived Ligand for the Oxidative Amination of Styrene

    Mannar R. Maurya
    Abstract The ligand H2sal-cys (I) derived from salicylaldehyde and L -cysteine has been covalently bonded to chloromethylated polystyrene cross-linked with 5,% divinylbenzene. Upon treatment with [VO(acac)2] in dimethylformamide (DMF) the polystyrene-bound ligand PS-H2sal-cys (II) gave the oxidovanadium(IV) complex, PS-[VO(sal-cys)·DMF] (1). The corresponding neat complex, [VO(sal-eta)]2 (2), has also been prepared similarly in methanol. These complexes have been characterised by IR, electronic, EPR spectroscopic studies, magnetic susceptibility measurements and thermal as well as scanning electron micrographs studies. Complex [VO(sal-eta)]2 exhibits a medium intensity band at 980 cm,1 in the IR spectrum due to ,(V=O) stretch. Broad features of the EPR spectrum for the neat complex along with magnetic susceptibility studies suggest the presence of antiferromagnetic exchange interaction between two vanadium centers in close proximity. Both complexes catalyze the oxidative amination of styrene, in mild basic conditions, with secondary amines (diethylamine, imidazole, and benzimidazole) and gave a mixture of two aminated products in good yields. Amongst the two aminated products, the anti-Markovnikov product is favored over the Markovnikov one due to the steric hindrance posed by the secondary amines. The polymer-anchored heterogeneous catalyst is free from leaching during catalytic action and recyclable.(© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2008) [source]

    Stable Platinum(0) Catalysts for Catalytic Hydrosilylation of Styrene and Synthesis of [Pt(Ar-bian)(,2 -alkene)] Complexes

    Jeroen W. Sprengers
    Abstract The use of alkenes and bidentate N-ligands in the platinum(0)-catalyzed hydrosilylation of styrene with triethylsilane has been evaluated. A number of bidentate N-ligands, phen, bpy, dafo, and phenyl-bian, were tested at various reaction temperatures using in situ formed catalysts with [Pt(nbe)3] as a precursor. The main conclusions are: (i) ligands, such as phen, which form stable platinum(0) complexes, give lower catalytic activities compared to the ligands which form less stable complexes; (ii) a small ligand effect is observed with dafo and phenyl-bian compared to [Pt(nbe)3], the precursor complex, displaying the lability of these ligands. The complex [Pt(nbe)3], that only has labile alkene ligands, is an active catalyst at low temperatures. At higher temperatures, the catalyst is no longer stable and a decrease in yield is observed. Several novel complexes have been synthesized: [Pt(m,m -(CF3)2 -C6H3 -bian)(tcne)], [Pt(m,m -(CF3)2 -C6H3 -bian)(ma)], [Pt(p -MeO-C6H4 -bian)(ma)], [Pt(p -MeO-C6H4 -bian)(dmfu)] and [Pt(phenyl-bian)(dmfu)]. Whereas the two [Pt(Ar-bian)(ma)] complexes are intrinsically more active than the two [Pt(Ar-bian)(dmfu)] complexes, the latter are much more stable, i.e. the nature of the alkene in these complexes is an important factor in determining their catalytic behavior. Compared to [Pt(Me-nq)(nbe)2], the two [Pt(Ar-bian)(dmfu)] complexes are much more stable resulting in significantly higher overall yields. (© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2003) [source]

    Syntheses of O6 -Alkyl- and Arylguanine Derivatives: Nucleobase Adducts Derived from Styrene 7,8- and 3,4-Oxides

    Jan Novák
    Abstract A series of O6 -alkyl and -arylguanine derivatives that may be formed in vivo after exposure to styrene has been prepared by reaction of 6-(4-aza-1-azoniabicyclo[2.2.2]octyl)-purine with alkoxides and aryloxides, respectively. Themonoprotected diols 2-allyloxy- or 2-benzyloxy-1-phenylethanol and 2-allyloxy- or 2-benzyloxy-2-phenylethanol were used as synthetic equivalents of styrene 7,8-oxide. 4-Vinylphenol, 2-(4-hydroxyphenyl)ethanol and 4-hydroxyphenylacetic acid were used as synthetic equivalents of arene oxide metabolites of styrene, i.,e., styrene 3,4-oxide, 4-(2-hydroxyethyl)benzene 1,2-oxide and 4-carboxymethylbenzene 1,2-oxide, respectively. (© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2006) [source]

    Highly Selective Cobalt-Catalyzed Hydrovinylation of Styrene

    Michiel M.
    Abstract Phosphine complexes of cobalt halide salts activated by diethylaluminum chloride are shown to yield highly active catalysts in the hydrovinylation of styrene, with unprecedented high selectivity to the desired product 3-phenyl-1-butene (3P1B). Double-bond isomerization, a common problem in codimerization reactions, only occurs after full conversion with these catalyst systems, even at elevated temperature. The most active catalysts are based on cobalt halide species combined with either C1 - or C2 -bridged diphosphines, heterodonor P,N or P,O ligands, flexible bidentate phosphine ligands or monodentate phosphine ligands. Kinetic investigations show an order >1 in catalyst, which indicates either the involvement of dinuclear species in the catalytic cycle or partial catalyst decomposition via a bimolecular pathway. [source]

    Styrene,butadiene block copolymer with high cis -1,4 microstructure

    Han Zhu
    Abstract The sequential block copolymerization of styrene (St) and butadiene (Bd) was carried out with an activated rare earth catalyst composed of catalyst neodymium tricarboxylate (Nd), cocatalyst Al(i-Bu)3 (Al), and chlorinating agent (Cl). The microstructure, composition, and morphology of the copolymer were characterized by FTIR, 1H NMR, 13C NMR, and TEM. The results show that styrene,butadiene diblock copolymer with high cis -1,4 microstructure of butadiene units (, 97 mol %) was synthesized. The cis -selectivity for Bd units was almost independent on the content of styrene units in the copolymer ranging from 18.1 mol % to 29.8 mol %. The phase-separated morphology of polystyrene (PS) domains of about 40 nm tethered by the elastomeric polybutadiene (PB) segments is observed. The PS- b - cis -PB copolymer could be used as an effective compatilizer for noncompatilized binary PS/cis -PB blends. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 2007 [source]

    Miscibility and rheological properties of poly(vinyl chloride)/styrene,acrylonitrile blends prepared by melt extrusion

    Hyun Sik Moon
    Abstract Styrene,acrylonitrile (SAN) with acrylonitrile (AN) concentrations of 11.6,26 wt % and ,-methylstyrene acrylonitrile (,MSAN) with a wide range of AN concentrations are miscible with poly(vinyl chloride) (PVC) through solution blending. Here we examine the rheological properties and miscibility of PVC/SAN and PVC/,MSAN blends prepared by melt extrusion for commercial applications. We have investigated the rheological properties of the blends with a rheometer and a melt indexer. The PVC/SAN and PVC/,MSAN blends have a low melting torque, a long degradation time, and a high melt index, and this means that they have better processability than pure PVC. The miscibility of the blends has been characterized with differential scanning calorimetry, dynamic mechanical thermal analysis, and advanced rheometrics expansion system analysis. The miscibility of the blends has also been characterized with scanning electron microscopy. The SAN series with AN concentrations of 24,31 wt % is immiscible with PVC by melt extrusion, whereas ,MSAN with 31 wt % AN is miscible with PVC, even when they are blended by melt extrusion, because of the strong interaction between PVC and ,MSAN. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 2007 [source]

    Chronic toxicity/oncogenicity study of styrene in cd-1 mice by inhalation exposure for 104 weeks

    George Cruzan
    Abstract Groups of 70 male and 70 female Charles River CD-1 mice were exposed whole body to styrene vapor at 0, 20, 40, 80 or 160 ppm 6 h per day 5 days per week for 98 weeks (females) or 104 weeks (males). The mice were observed daily; body weights, food and water consumption were measured periodically, a battery of hematological and clinical pathology examinations were conducted at weeks 13, 26, 52, 78 and 98 (females)/104 (males). Ten mice of each gender per group were pre-selected for necropsy after 52 and 78 weeks of exposure and the survivors of the remaining 50 of each gender per group were necropsied after 98 or 104 weeks. An extensive set of organs from the control and high-exposure mice were examined histopathologically, whereas target organs, gross lesions and all masses were examined in all other groups. Styrene had no effect on survival in males. Two high-dose females died (acute liver toxicity) during the first 2 weeks; the remaining exposed females had a slightly higher survival than control mice. Levels of styrene and styrene oxide (SO) in the blood at the end of a 6 h exposure during week 74 were proportional to exposure concentration, except that at 20 ppm the SO level was below the limit of detection. There were no changes of toxicological significance in hematology, clinical chemistry, urinalysis or organ weights. Mice exposed to 80 or 160 ppm gained slightly less weight than the controls. Styrene-related non-neoplastic histopathological changes were found only in the nasal passages and lungs. In the nasal passages of males and females at all exposure concentrations, the changes included respiratory metaplasia of the olfactory epithelium with changes in the underlying Bowman's gland; the severity increased with styrene concentration and duration of exposure. Loss of olfactory nerve fibers was seen in mice exposed to 40, 80 or 160 ppm. In the lungs, there was decreased eosinophilia of Clara cells in the terminal bronchioles and bronchiolar epithelial hyperplasia extending into alveolar ducts. Increased tumor incidence occurred only in the lung. The incidence of bronchioloalveolar adenomas was significantly increased in males exposed to 40, 80 or 160 ppm and in females exposed to 20, 40 and 160 ppm. The increase was seen only after 24 months. In females exposed to 160 ppm, the incidence of bronchiolo-alveolar carcinomas after 24 months was significantly greater than in the controls. No difference in lung tumors between control and styrene-exposed mice was seen in the intensity or degree of immunostaining, the location of tumors relative to bronchioles or histological type (papillary, solid or mixed). It appears that styrene induces an increase in the number of lung tumors seen spontaneously in CD-1 mice. Copyright © 2001 John Wiley & Sons, Ltd. [source]

    Millisecond catalytic reforming of monoaromatics over noble metals

    AICHE JOURNAL, Issue 4 2010
    C. M. Balonek
    Abstract The millisecond autothermal reforming of benzene, toluene, ethylbenzene, cumene, and styrene were independently studied over five noble metal-based catalysts: Pt, Rh, Rh/,-Al2O3, Rh,Ce, and Rh,Ce/,-Al2O3, as a function of carbon-to-oxygen feed ratio. The Rh,Ce/,-Al2O3 catalyst exhibited the highest feedstock conversion as well as selectivities to both synthesis gas and hydrocarbon products (lowest selectivities to H2O and CO2). Experimental results demonstrate a high stability of aromatic rings within the reactor system. Benzene and toluene seem to react primarily heterogeneously, producing only syngas and combustion products. Ethylbenzene and cumene behaved similarly, with higher conversions than benzene and toluene, and high product selectivity to styrene, likely due to homogeneous reactions involving their alkyl groups. Styrene exhibited low conversions over Rh,Ce/,-Al2O3, emphasizing the stability of styrene in the reactor system. © 2009 American Institute of Chemical Engineers AIChE J, 2009 [source]

    Styrene 4-vinylbenzocyclobutene copolymer for microelectronic applications

    Ying-Hung So
    Abstract Styrene and 4-vinylbenzocyclobutene (vinyl-BCB) random copolymers were prepared by free radical polymerization and studied for suitability as a dielectric material for microelectronic applications. The percentage of vinyl-BCB in the copolymer was varied from 0 to 26 mol % to optimize the physical and mechanical properties of the cured copolymer as well as the cost. Copolymer in which 22 mol % of vinyl-BCB was incorporated along with styrene produced a thermoset polymer which, after cure, did not show a Tg before decomposition at about 350 °C. The polymeric material has a very low dielectric constant, dissipation factor, and water uptake. The fracture toughness of the copolymer was improved with the addition of 20 wt % of a star-shaped polystyrene- block -polybutadiene. Blends of the poly(styrene- co -vinyl-BCB) with the thermoplastic elastomer provided material that maintained high Tg of the cured copolymer with only a slight decrease in thermal stability. The crosslinked styrenic polymer and toughened blends possess many properties that are desirable for high frequency-high speed mobile communication applications. © 2008 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 46: 2799,2806, 2008 [source]

    Termination Rate Coefficients for Radical Homopolymerization of Methyl Methacrylate and Styrene at Low Conversion,

    David R. Taylor
    Abstract A comprehensive and systematic study of overall termination rate coefficients, kt, in low-conversion radical (homo)polymerization of methyl methacrylate and styrene is presented. Values of kt were determined by gravimetric analysis of steady-state experiments, employing 2,2,-azoisobutyronitrile as initiator. The values delivered by this simple method were found to be in qualitative and quantitative agreement with those from more modern and sophisticated techniques for measuring kt. Accordingly, correlations for bulk, low-conversion kt as a function of temperature are given for each monomer. The effects of initiator concentration, cI, and temperature on bulk kt were studied in a controlled way for both monomers. Additionally, ethyl benzene was used as solvent in order to investigate rigorously the effect of monomer concentration, cM, on styrene kt. The trends found by these systematic studies were considered in the light of what is known about the chain-length dependence of termination. Styrene's behavior was always found to be qualitatively in accord with expectation, although the variations of kt with cI and cM were not as strong as should be the case. However its activation energy, 15,kJ,·,mol,1, is shown to be almost perfectly in agreement with theory. Methyl methacrylate, on the other hand, is recalcitrant in that its overall kt does not make manifest the chain-length dependent termination that has been directly measured by other techniques. Possible reasons for these discrepancies are discussed, as are reasons for the difference in values between kt for the two monomers. On the latter topic it is concluded likely that the chain-length dependence of termination at short chain lengths is primarily responsible for styrene having kt that is higher by a factor of about 3, with there also being a contribution that arises from styrene's slower propagation. [source]

    Synthesis of Polystyrene- block -Poly(methyl methacrylate) with Fluorene at the Junction: Sequential Anionic and Controlled Radical Polymerization from a Single Carbon

    Nathan D. Contrella
    Abstract Polystyrene- block -poly(methyl methacrylate) (PS- b -PMMA) has been synthesized by sequential anionic and reverse atom transfer radical polymerization (ATRP) or a variation of nitroxide mediated polymerization (NMP) from a single initiating site, specifically the 9-carbon on 2,7-dibromofluorene or fluorene. The addition of the second arm (PS) relied on thermal decomposition of 2,2,-azoisobutyronitrile (AIBN) to generate radicals, abstracting the 9-H on the polymer-bound fluorene species to form the initiating radical. Styrene was not present in the reaction mixture when AIBN was decomposed, preventing competition between addition across the monomeric alkene and hydrogen abstraction from the fluorene. After 1,h, styrene was introduced and mediation of the subsequent radical polymerization was achieved by the presence of CuCl2/ligand or TEMPO. Characterization of the diblock copolymers by gel permeation chromatography (GPC) revealed substantial shifts in number average molecular weight () values compared to the anionically prepared PMMA macroinitiator, while polydispersity indices (PDI's) remained relatively low (typically,<,1.5). Characterization by UV detection with GPC (at 310,nm) verified that the diblock polymer is chromophore-bound, which was further verified by UV-vis spectroscopy of the isolated diblock. [source]

    Gelation and Hollow Particle Formation in Nitroxide-Mediated Radical Copolymerization of Styrene and Divinylbenzene in Miniemulsion

    Per B. Zetterlund
    Abstract Network formation in the nitroxide-mediated cross-linking copolymerization of styrene and divinylbenzene (3 or 8.2 mol-% relative to total monomer) using the nitroxide 2,2,6,6-tetramethylpiperidinyl-1-oxy (TEMPO) at 125,°C can proceed markedly differently in aqueous miniemulsion compared to the corresponding solution polymerization depending on the organic-phase composition. When the organic phase comprises 54 vol-% of the hydrophobe tetradecane, gelation occurs at much lower conversion in miniemulsion than in solution, and at significantly lower conversion than predicted by Flory,Stockmayer gelation theory. This is proposed to be a result of an effect of the oil,water interface, whereby the concentration of polymer with pendant unsaturations is higher near the interface than in the particle interior. [source]

    Novel Amphiphilic Styrene-Based Block Copolymers for Induced Surface Reconstruction

    Lutz Funk
    Abstract This paper describes the synthesis of amphiphilic block copolymers by living radical polymerization (NMP) of new styrene-like monomers. The polar monomers (ethylene oxide side chains and free hydroxyl- or amino-groups after deprotection) were polymerized in a "protected form" to adjust the solubility of the monomers. In this way high molar mass polymers with a narrow polydispersity (around or below 1.2) were accessible. In the bulk state hydrophobic and hydrophilic domains demix. By exposing thin films of these polymers to vacuum (air) or alternatively to water or a hydrophilic surface it becomes possible to switch the surface polarity reversibly between contact angles of about 105° and 83° as a result of surface reconstruction. Through side chains of different length and with different functionalities, it was possible to adjust the glass transition temperatures to values between ,2,°C to 140,°C for the hydrophilic blocks and ,30,°C to 100,°C for the hydrophobic block. The wide range of the glass temperatures allowed it to find a block copolymer system with a slow kinetic concerning the surface reconstruction process, so that a mechanistic examination of the process by AFM was possible. It got, thereby, possible to detect the break-up of the hydrophobic surface lamella and the upfold of the hydrophilic lamella in contact with water. [source]

    N -Oxyl-Controlled Radical Copolymerization of Styrene with Ethyl , -Cyanocinnamate

    Andreas Bartsch
    Abstract Summary: The block copolymers of styrene and ethyl , -cyanocinnamate were prepared in dioxane and xylene with TEMPO-capped polystyrene (PSTEMPO) as macroinitiator. The copolymerizations were carried out at 125,°C and 135,°C. The reactivity ratios were determined according to Kelen Tüdos and compared with the reactivity ratios from the radical copolymerization of styrene and ethyl , -cyanocinnamate determined by Kohn et al. The influence of the comonomer ethyl , -cyanocinnamate on the glass transition temperature was studied in comparison with the corresponding homopolystyrene. Plots of conversion versus molecular weight distributions of the polymerizations with styrene at 125,°C. [source]

    High-Temperature Propagation and Termination Kinetics of Styrene to High Conversion Investigated by Electron Paramagnetic Resonance Spectroscopy

    Per B. Zetterlund
    Abstract Summary: The free radical bulk polymerization of styrene at 120,°C has been investigated over almost the entire conversion range using electron paramagnetic resonance spectroscopy, Fourier-transform near-infrared spectroscopy and gel permeation chromatography. The free radical concentration went through a sharp maximum that coincided with the peak in the rate of polymerization during the gel effect, and shifted to higher conversion with increasing initiator concentration. The termination rate coefficient (kt), decoupled from the initiator efficiency (f) by use of the instantaneous degree of polymerization, remained close to constant up to as high as approximately 80% conversion, at which a dramatic decrease occurred. Both the propagation rate coefficient (kp) and f fell orders of magnitude near 80% conversion in spite of the temperature being above the glass transition temperature of the system. The value of kp increased with the initiator concentration at a given conversion in the highest (diffusion-controlled) conversion range. Termination rate coefficient (kt) versus conversion for bulk free radical polymerization of St initiated by TBP at 120,°C. [TBP],=,0.15 (,), 0.10 (,) and 0.05 M (). [source]

    Kinetics of Miniemulsion Polymerization of Styrene in the Presence of Organoclays

    Zhaohui Tong
    Abstract The impacts of nanoclays on the miniemulsion polymerization kinetics of styrene were studied. It was found that both RP and the fractional conversion decreased upon increasing the organoclay content in the miniemulsion system. In the presence of nanoclay the molecular weight of polystyrene nanoclay composite is lower and the particle size polydispersity of the final composite latex is greater than that of pure styrene miniemulsion polymerization. The effect of the nanoclays is mainly caused by the destabilization of the miniemulsion by the organoclay particles. The increase in the monomer viscosity and the decrease in the diffusion rate of the monomer and the living polymer inside the monomer droplet also accounts for the reduction in the polymerization rate. [source]

    Microwave-Assisted Free Radical Copolymerizations of Styrene and Methyl Methacrylate

    Heiner Stange
    Abstract Free radical copolymerizations of styrene and MMA were performed in toluene and DMF as solvents using different peroxide initiators with and without microwave irradiation. A general trend showed significant solvent dependence of monomer conversion rate only for copolymerizations initiated by tert -butyl perbenzoate in DMF compared to toluene but nearly no impact for copolymerizations initiated by dicumyl peroxide and dibenzoyl peroxide. Significant variations in copolymer composition were not observed for reactions under conventional heating compared to microwave irradiation. It was concluded that enhanced initiator decomposition under microwave irradiation in DMF accelerate polymerization of styrene and MMA by formation of larger amount of initiator radicals. [source]

    Modeling of the Nitroxide-Mediated Radical Copolymerization of Styrene and Divinylbenzene

    Julio C. Hernández-Ortiz
    Abstract A mathematical model for the copolymerization kinetics with crosslinking of vinyl/divinyl monomers in the presence of nitroxide controllers has been developed and validated using experimental data of TEMPO-mediated copolymerization of styrene (STY) and divinylbenzene (DVB). Polymerization rate, molecular weight development, gelation point, evolution of sol and gel weight fractions, crosslink density, and copolymer composition, as well as concentrations of the species participating in the reaction mechanism can be calculated with the model. Diffusion-controlled effects were assessed and found unimportant. The presence of nitroxide controllers seems to favor the production of more homogeneous polymer networks, but this effect decreases as the initial fraction of crosslinker is increased. [source]

    Kinetics and Molecular Weight Development of Dithiolactone-Mediated Radical Polymerization of Styrene

    Jesús Guillermo Soriano-Moro
    Abstract Calculations of polymerization kinetics and molecular weight development in the dithiolactone-mediated polymerization of styrene at 60,°C, using 2,2,-azobisisobutyronitrile (AIBN) as initiator and , -phenyl- , -butirodithiolactone (DTL1) as controller, are presented. The calculations were based on a polymerization mechanism based on the persistent radical effect, considering reverse addition only, implemented in the PREDICI® commercial software. Kinetic rate constants for the reverse addition step were estimated. The equilibrium constant (K,=,kadd/k -add) fell into the range of 105,106 L,·,mol,1. Fairly good agreement between model calculations and experimental data was obtained. [source]

    Modeling of Polymerization Kinetics and Molecular Weight Development in the Microwave-Activated Nitroxide-Mediated Radical Polymerization of Styrene

    Jorge J. Hernández-Meza
    Abstract Calculations of the polymerization rate and molecular weight development in the nitroxide-mediated radical polymerization (NMRP) of styrene (STY), using hydroxyl-TEMPO and dibenzoyl peroxide (BPO), and activated by microwave irradiation (MI), are presented. The calculations are based on a kinetic model developed in our group. Microwave activation is modeled by three approaches: microwave-activated production of free radicals from monomer molecules, microwave-enhanced thermal initiation, and microwave-enhanced dormant polymer activation. The results obtained are compared against experimental data from the literature. The first approach is the most adequate. The NMRP of STY using TEMPO, BPO, and conductive heating, and the NMRP of STY activated by MI, without initiator, are also analyzed as reference cases. [source]

    An Experimental Study on the Free-Radical Copolymerization Kinetics with Crosslinking of Styrene and Divinylbenzene in Supercritical Carbon Dioxide

    Pedro R. García-Morán
    Abstract A study on the effect of process conditions and composition of the reacting mixture on the kinetics and particle properties in the copolymerization of styrene and divinylbenzene in supercritical carbon dioxide is presented. Polystyrene -block- polydimethylsiloxane and Krytox 257 FSL (Dupont) were used as stabilizers, and their performance compared. A 38 mL, high-pressure view cell, equipped with one frontal and two lateral sapphire windows, was used as the reacting vessel. The polymer product was characterized for total monomer conversion, gel content, molecular weight averages of the sol fraction and particle size distribution. Acceptable polymerization rates and partially-agglomerated spherical particles were produced under the conditions tested. [source]

    A Comparison of Modeling Approaches for Dispersion Homopolymerization of MMA and Styrene in Supercritical CO2

    Iraís A. Quintero-Ortega
    Abstract A comparison of kinetic models for dispersion polymerization of MMA and styrene in supercritical CO2 is presented. The limiting case of solution polymerization, as a simplified case, was also addressed. Calculation of the partition of components between the continuous and dispersed phases was emphasized. Experimental data for the solution and dispersion polymerizations of styrene and MMA, using different types of stabilizers, were used to guide the study. Although all the models analyzed can be considered as "adequate" in representing the behavior of the system, some of their strengths and drawbacks have been highlighted. [source]

    Atom-Transfer Radical Batch and Semibatch Polymerization of Styrene

    Yao Fu
    Abstract Batch and semibatch styrene polymerizations are carried out using a heterogeneous ATRP catalyst system that provides excellent molecular-weight control. The observed initiator efficiency is lower for semibatch operation due to the high initiator concentrations required to make a low-MW polymer. Experiments verified that the insoluble metal complex does not participate in the polymerization and that Cu(I) solubility is an order of magnitude higher than that of Cu(II). A mechanistic model, using kinetic coefficients from literature and the solubility data from this study, provides a good representation of the experimental results. [source]

    Aluminate and Magnesiate Complexes as Propagating Species in the Anionic Polymerization of Styrene and Dienes

    Alain Deffieux
    Abstract The influence of MgR2 and AlR3 additives on alkyllithium initiators in the anionic polymerization of butadiene has been investigated in non polar solvents. A strong decrease of the diene polymerization rate in the presence of the two Lewis acids was observed, similarly to that observed in the retarded anionic polymerisation of styrene. With n,s-Bu2Mg, the percentage of 1,2 vinyl units increases with the [Mg]/[Li] ratio. This behavior is specific to magnesium derivatives bearing secondary alkyl groups and likely results from the additional complexation of lithium species by free dialkylmagnesium and/or a 1,4- to 1,2- chain end isomerization process during chain exchanges between polybutadienyl active chains and dormant ones attached to magnesium species. These reversible exchanges also lead to the formation of one supplementary chain by initial dialkyl magnesium which acts as reversible chain transfer agent. On the contrary with the R3Al/RLi systems the number of chains is only determined by the concentration of initial alkyllithium and no modification of the polybutadiene microstructure compared to lithium initiators (1,4 units = 80%) is noticed. Dialkyl magnesiate complexes with alkali metal derivatives (i.e. alkoxide) are also able to influence the stereochemistry of the styrene insertion during the propagation reaction. Polystyrenes with different tacticities ranging from predominantly isotactic (85% triad iso) to syndiotactic (80% triad syndio) can be obtained with these initiators. [source]

    Sol MWD During Styrene, Vinyl Acetate, Methyl Methacrylate, and Butyl Acrylate Homopolymerization: A Numerical Study Using the NFT Approach

    Bibiana Alejandra Yáńez-Martínez
    Abstract Complete parameter sensitivity analyses using the numerical fractionation technique are presented for the cases of homopolymerization with chain transfer to polymer and termination by combination. Also, using reported values for the kinetic rate constants associated with the linear and non-linear homopolymerizations of styrene, vinyl acetate, methyl methacrylate and butyl acrylate, overall molecular weight distributions and averages of the MWD were calculated using the NFT. Good agreement with the expected behavior, with MMA and STY not gelling while BA and VAc do, was obtained. It is concluded that the NFT produces coherent and reliable performance for known polymerization systems, whether linear or non-linear. [source]

    On the Nitroxide Quasi-Equilibrium in the Alkoxyamine-Mediated Radical Polymerization of Styrene

    Enrique Saldívar-Guerra
    Abstract Summary: The range of validity of two popular versions of the nitroxide quasi-equilibrium (NQE) approximation used in the theory of kinetics of alkoxyamine mediated styrene polymerization, are systematically tested by simulation comparing the approximate and exact solutions of the equations describing the system. The validity of the different versions of the NQE approximation is analyzed in terms of the relative magnitude of (dN/dt)/(dP/dt). The approximation with a rigorous NQE, kc[P][N],=,kd[PN], where P, N and PN are living, nitroxide radicals and dormant species respectively, with kinetic constants kc and kd, is found valid only for small values of the equilibrium constant K (10,11,10,12 mol,·,L,1) and its validity is found to depend strongly of the value of K. On the other hand, the relaxed NQE approximation of Fischer and Fukuda, kc[P][N],=,kd[PN]0 was found to be remarkably good up to values of K around 10,8 mol,·,L,1. This upper bound is numerically found to be 2,3 orders of magnitude smaller than the theoretical one given by Fischer. The relaxed NQE is a better one due to the fact that it never completely neglects dN/dt. It is found that the difference between these approximations lies essentially in the number of significant figures taken for the approximation; still this subtle difference results in dramatic changes in the predicted course of the reaction. Some results confirm previous findings, but a deeper understanding of the physico-chemical phenomena and their mathematical representation and another viewpoint of the theory is offered. Additionally, experiments and simulations indicate that polymerization rate data alone are not reliable to estimate the value of K, as recently suggested. Validity of the rigorous nitroxide quasi-equilibrium assumption as a function of the nitroxide equilibrium constant. [source]